4,4′-(m-Phenyl­enedioxy­dimethyl­ene)dipyridinium dinitrate trihydrate

In the title compound, C₁₈H₁₈N₂O₂²⁺·2NO₃⁻·3H₂O, all bond lengths and angles in the diprotonated 1,3-bis­(4-pyridylmeth­oxy)benzene cation are normal. The mol­ecular skeleton of the cation is approximately planar; the central benzene ring makes dihedral angles of 8.98 (11) and 1.30 (12)° with the two outer pyridine rings. In the crystal structure, an extensive network of inter­molecular of N—H...O and O—H...O hydrogen bonds stabilizes the packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.153
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem...          a

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N4
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              N O3

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b).

4,4'-(m-Phenylenendioxydimethylene)dipyridinium dinitrate trihydrate

Crystal data

C18H18N2O2^2+·2NO3^−·3H2O	Z = 2
Mr = 472.41	F(000) = 496
Triclinic, P1	Dx = 1.421 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1509 (14) Å	Cell parameters from 7667 reflections
b = 10.821 (2) Å	θ = 6.3–55.0°
c = 15.214 (3) Å	µ = 0.12 mm^−1
α = 110.25 (3)°	T = 293 K
β = 90.70 (3)°	Block, colourless
γ = 90.09 (3)°	0.38 × 0.22 × 0.22 mm
V = 1104.4 (4) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	4958 independent reflections
Radiation source: fine-focus sealed tube	3347 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→14
Tmin = 0.957, Tmax = 0.974	l = −19→19
10880 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0784P)^2 + 0.1778P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.004
4958 reflections	Δρmax = 0.59 e Å^−3
307 parameters	Δρmin = −0.34 e Å^−3
15 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.9071 (2)	1.10299 (15)	1.15629 (11)	0.0402 (4)
O2	0.6013 (2)	0.94988 (15)	0.85099 (11)	0.0406 (4)
N1	1.1767 (3)	1.0057 (2)	1.41963 (15)	0.0431 (5)
N2	0.3429 (3)	0.5883 (2)	0.59018 (15)	0.0440 (5)
C2	1.0395 (3)	0.8782 (2)	1.27667 (17)	0.0405 (5)
H2	1.0066	0.7960	1.2339	0.049*
C8	0.8412 (3)	1.2435 (2)	1.07504 (17)	0.0400 (5)
H8	0.8980	1.3106	1.1240	0.048*
C17	0.3715 (4)	0.7157 (2)	0.60651 (17)	0.0443 (6)
H17	0.3316	0.7524	0.5626	0.053*
C7	0.8310 (3)	1.1169 (2)	1.07744 (15)	0.0320 (5)
C12	0.7526 (3)	1.0148 (2)	1.00396 (14)	0.0317 (5)
H11	0.7486	0.9297	1.0055	0.038*
C18	0.4592 (3)	0.7935 (2)	0.68729 (16)	0.0383 (5)
H18	0.4807	0.8824	0.6983	0.046*
C6	0.8934 (3)	0.9798 (2)	1.16897 (16)	0.0343 (5)
H7	0.9486	0.9114	1.1164	0.041*
H6	0.7632	0.9572	1.1730	0.041*
C10	0.6834 (3)	1.1691 (2)	0.92507 (17)	0.0397 (5)
H10	0.6311	1.1866	0.8744	0.048*
C3	0.9957 (3)	0.9910 (2)	1.25791 (15)	0.0331 (5)
C14	0.5154 (3)	0.7367 (2)	0.75275 (15)	0.0336 (5)
C13	0.6123 (3)	0.8159 (2)	0.84196 (16)	0.0354 (5)
H12	0.5527	0.8018	0.8947	0.042*
H13	0.7421	0.7895	0.8408	0.042*
C9	0.7655 (3)	1.2687 (2)	0.99861 (18)	0.0428 (6)
H9	0.7701	1.3537	0.9969	0.051*
C15	0.4825 (4)	0.6041 (2)	0.73284 (17)	0.0433 (6)
H14	0.5205	0.5641	0.7751	0.052*
C11	0.6800 (3)	1.0423 (2)	0.92801 (15)	0.0318 (5)
C4	1.0473 (3)	1.1120 (2)	1.32285 (16)	0.0372 (5)
H3	1.0207	1.1895	1.3117	0.045*
C5	1.1378 (3)	1.1161 (2)	1.40359 (17)	0.0426 (6)
H4	1.1724	1.1969	1.4477	0.051*
C16	0.3944 (4)	0.5316 (3)	0.65142 (18)	0.0482 (6)
H15	0.3703	0.4426	0.6386	0.058*
C1	1.1311 (4)	0.8877 (2)	1.35815 (18)	0.0451 (6)
H1	1.1615	0.8119	1.3707	0.054*
O3	0.1734 (3)	0.42270 (17)	0.43297 (13)	0.0560 (5)
O4	0.1649 (4)	0.6035 (2)	0.40633 (17)	0.0746 (7)
O5	0.0465 (3)	0.4278 (2)	0.30593 (15)	0.0654 (6)
N3	0.1266 (3)	0.4866 (2)	0.38124 (15)	0.0443 (5)
O11	0.6513 (3)	0.6131 (2)	0.13588 (15)	0.0757 (7)
H23	0.6119	0.6767	0.1824	0.113*
H24	0.7660	0.5987	0.1438	0.113*
O9	0.0159 (3)	0.56006 (19)	0.17384 (15)	0.0627 (6)
H19	0.0178	0.5289	0.2181	0.094*
H20	0.1074	0.5269	0.1385	0.094*
O10	0.3302 (3)	0.4424 (3)	0.06559 (17)	0.0779 (7)
H21	0.3181	0.4255	0.0069	0.117*
H22	0.4303	0.4867	0.0843	0.117*
H16	0.293 (4)	0.538 (3)	0.533 (2)	0.072 (10)*
H5	1.237 (4)	1.009 (3)	1.478 (2)	0.071 (9)*
O6	1.4348 (3)	1.1420 (2)	1.71523 (14)	0.0648 (6)
O8	1.3346 (4)	1.2101 (2)	1.60661 (18)	0.0818 (7)
O7	1.3457 (3)	1.00512 (18)	1.58222 (13)	0.0560 (5)
N4	1.3750 (3)	1.1202 (2)	1.63499 (15)	0.0435 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0546 (10)	0.0332 (8)	0.0335 (9)	−0.0092 (7)	−0.0151 (7)	0.0128 (7)
O2	0.0538 (10)	0.0353 (8)	0.0301 (8)	−0.0015 (7)	−0.0140 (7)	0.0087 (7)
N1	0.0492 (12)	0.0491 (12)	0.0347 (11)	−0.0040 (10)	−0.0085 (9)	0.0195 (10)
N2	0.0498 (12)	0.0419 (11)	0.0324 (11)	−0.0028 (9)	−0.0090 (9)	0.0031 (9)
C2	0.0466 (13)	0.0342 (12)	0.0401 (13)	−0.0019 (10)	−0.0038 (10)	0.0120 (10)
C8	0.0471 (13)	0.0319 (11)	0.0364 (13)	−0.0034 (10)	−0.0066 (10)	0.0063 (10)
C17	0.0534 (14)	0.0438 (13)	0.0338 (13)	0.0047 (11)	−0.0100 (11)	0.0113 (10)
C7	0.0328 (10)	0.0333 (11)	0.0290 (11)	0.0001 (9)	−0.0031 (8)	0.0097 (9)
C12	0.0332 (10)	0.0304 (11)	0.0297 (11)	−0.0003 (9)	−0.0017 (8)	0.0080 (9)
C18	0.0480 (13)	0.0320 (11)	0.0337 (12)	0.0007 (10)	−0.0052 (10)	0.0101 (9)
C6	0.0382 (11)	0.0316 (11)	0.0328 (12)	−0.0045 (9)	−0.0062 (9)	0.0109 (9)
C10	0.0482 (13)	0.0372 (12)	0.0360 (13)	0.0053 (10)	−0.0043 (10)	0.0158 (10)
C3	0.0329 (10)	0.0357 (11)	0.0306 (11)	−0.0044 (9)	−0.0021 (9)	0.0113 (9)
C14	0.0348 (11)	0.0347 (11)	0.0292 (11)	0.0023 (9)	−0.0015 (9)	0.0085 (9)
C13	0.0402 (11)	0.0332 (11)	0.0312 (11)	0.0007 (9)	−0.0068 (9)	0.0093 (9)
C9	0.0540 (14)	0.0301 (11)	0.0459 (14)	0.0011 (11)	−0.0041 (11)	0.0153 (10)
C15	0.0559 (14)	0.0379 (13)	0.0369 (13)	−0.0041 (11)	−0.0072 (11)	0.0144 (10)
C11	0.0329 (10)	0.0320 (11)	0.0279 (11)	−0.0005 (9)	−0.0024 (8)	0.0071 (8)
C4	0.0453 (12)	0.0338 (11)	0.0334 (12)	−0.0035 (10)	−0.0061 (10)	0.0128 (9)
C5	0.0519 (14)	0.0400 (13)	0.0344 (13)	−0.0104 (11)	−0.0095 (10)	0.0114 (10)
C16	0.0623 (16)	0.0358 (12)	0.0423 (14)	−0.0046 (11)	−0.0074 (12)	0.0083 (11)
C1	0.0545 (14)	0.0418 (13)	0.0437 (14)	0.0037 (11)	−0.0037 (11)	0.0210 (11)
O3	0.0813 (13)	0.0419 (10)	0.0437 (10)	−0.0064 (9)	−0.0195 (9)	0.0142 (8)
O4	0.1176 (19)	0.0401 (11)	0.0679 (15)	−0.0136 (11)	−0.0225 (13)	0.0220 (10)
O5	0.0732 (13)	0.0696 (14)	0.0515 (12)	−0.0137 (11)	−0.0283 (10)	0.0196 (11)
N3	0.0465 (11)	0.0439 (12)	0.0405 (12)	−0.0014 (9)	−0.0067 (9)	0.0124 (10)
O11	0.0790 (15)	0.0746 (15)	0.0592 (14)	0.0124 (12)	−0.0180 (11)	0.0057 (11)
O9	0.0754 (13)	0.0497 (11)	0.0621 (13)	0.0066 (10)	−0.0066 (11)	0.0186 (10)
O10	0.0770 (15)	0.0996 (18)	0.0699 (15)	0.0125 (13)	0.0046 (12)	0.0453 (14)
O6	0.0708 (13)	0.0784 (15)	0.0407 (11)	0.0037 (11)	−0.0178 (9)	0.0156 (10)
O8	0.1139 (12)	0.0596 (10)	0.0793 (11)	−0.0033 (9)	−0.0209 (9)	0.0341 (9)
O7	0.0830 (13)	0.0415 (10)	0.0430 (11)	−0.0002 (9)	−0.0146 (9)	0.0144 (8)
N4	0.0454 (11)	0.0486 (12)	0.0381 (12)	−0.0002 (9)	−0.0070 (9)	0.0173 (10)

Geometric parameters (Å, º)

O1—C7	1.366 (2)	C10—C11	1.388 (3)
O1—C6	1.415 (3)	C10—H10	0.9300
O2—C11	1.364 (3)	C3—C4	1.386 (3)
O2—C13	1.411 (3)	C14—C15	1.380 (3)
N1—C5	1.329 (3)	C14—C13	1.492 (3)
N1—C1	1.332 (3)	C13—H12	0.9700
N1—H5	0.97 (3)	C13—H13	0.9700
N2—C17	1.328 (3)	C9—H9	0.9300
N2—C16	1.330 (3)	C15—C16	1.361 (3)
N2—H16	0.91 (4)	C15—H14	0.9300
C2—C1	1.367 (3)	C4—C5	1.368 (3)
C2—C3	1.381 (3)	C4—H3	0.9300
C2—H2	0.9300	C5—H4	0.9300
C8—C7	1.385 (3)	C16—H15	0.9300
C8—C9	1.387 (3)	C1—H1	0.9300
C8—H8	0.9300	O3—N3	1.257 (3)
C17—C18	1.369 (3)	O4—N3	1.219 (3)
C17—H17	0.9300	O5—N3	1.235 (3)
C7—C12	1.383 (3)	O11—H23	0.8500
C12—C11	1.385 (3)	O11—H24	0.8500
C12—H11	0.9300	O9—H19	0.8500
C18—C14	1.395 (3)	O9—H20	0.8499
C18—H18	0.9300	O10—H21	0.8501
C6—C3	1.498 (3)	O10—H22	0.8501
C6—H7	0.9700	O6—N4	1.231 (3)
C6—H6	0.9700	O8—N4	1.226 (3)
C10—C9	1.380 (3)	O7—N4	1.242 (3)
C7—O1—C6	119.20 (17)	C15—C14—C13	120.0 (2)
C11—O2—C13	118.92 (17)	C18—C14—C13	121.3 (2)
C5—N1—C1	121.7 (2)	O2—C13—C14	108.00 (17)
C5—N1—H5	120.2 (19)	O2—C13—H12	110.1
C1—N1—H5	118.1 (19)	C14—C13—H12	110.1
C17—N2—C16	121.9 (2)	O2—C13—H13	110.1
C17—N2—H16	118 (2)	C14—C13—H13	110.1
C16—N2—H16	120 (2)	H12—C13—H13	108.4
C1—C2—C3	119.9 (2)	C10—C9—C8	120.8 (2)
C1—C2—H2	120.1	C10—C9—H9	119.6
C3—C2—H2	120.1	C8—C9—H9	119.6
C7—C8—C9	119.1 (2)	C16—C15—C14	120.2 (2)
C7—C8—H8	120.5	C16—C15—H14	119.9
C9—C8—H8	120.5	C14—C15—H14	119.9
N2—C17—C18	120.7 (2)	O2—C11—C12	123.9 (2)
N2—C17—H17	119.6	O2—C11—C10	114.70 (19)
C18—C17—H17	119.6	C12—C11—C10	121.4 (2)
O1—C7—C12	124.26 (19)	C5—C4—C3	119.1 (2)
O1—C7—C8	114.42 (19)	C5—C4—H3	120.4
C12—C7—C8	121.3 (2)	C3—C4—H3	120.4
C7—C12—C11	118.4 (2)	N1—C5—C4	120.6 (2)
C7—C12—H11	120.8	N1—C5—H4	119.7
C11—C12—H11	120.8	C4—C5—H4	119.7
C17—C18—C14	118.6 (2)	N2—C16—C15	119.9 (2)
C17—C18—H18	120.7	N2—C16—H15	120.0
C14—C18—H18	120.7	C15—C16—H15	120.0
O1—C6—C3	107.73 (17)	N1—C1—C2	120.0 (2)
O1—C6—H7	110.2	N1—C1—H1	120.0
C3—C6—H7	110.2	C2—C1—H1	120.0
O1—C6—H6	110.2	O4—N3—O5	122.4 (2)
C3—C6—H6	110.2	O4—N3—O3	118.9 (2)
H7—C6—H6	108.5	O5—N3—O3	118.7 (2)
C9—C10—C11	118.9 (2)	H23—O11—H24	110.4
C9—C10—H10	120.5	H19—O9—H20	107.4
C11—C10—H10	120.5	H21—O10—H22	108.4
C2—C3—C4	118.6 (2)	O8—N4—O6	121.6 (2)
C2—C3—C6	119.5 (2)	O8—N4—O7	118.4 (2)
C4—C3—C6	121.8 (2)	O6—N4—O7	119.9 (2)
C15—C14—C18	118.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H23···O6^i	0.85	2.07	2.901 (3)	166
O11—H24···O9^ii	0.85	1.92	2.767 (3)	173
O9—H19···O5	0.85	2.01	2.849 (3)	170
O9—H20···O10	0.85	1.99	2.835 (3)	174
O10—H21···O11^iii	0.85	2.08	2.917 (3)	168
O10—H22···O11	0.85	2.05	2.896 (4)	173
N2—H16···O3	0.91 (4)	1.81 (4)	2.712 (3)	169 (3)
N1—H5···O7	0.97 (3)	1.77 (3)	2.741 (3)	176 (3)

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x+1, y, z; (iii) −x+1, −y+1, −z.